Derivative of naphthalocyanine containing perfluoroalkyl group, process for preparing the same and optical recording medium

ABSTRACT

A derivative of naphthalocyanine containing a perfluoroalkyl group and having a particular structure for ensuring excellent weather-proof properties, extremely high solubility in various solvents and capability of forming a film, and an optical recording medium prepared by using the derivative and capable of recording while using a focused beam of a semiconductor laser or the like. The derivative of naphthalocyanine containing a perfluoroalkyl group may be prepared by reacting a perfluoroalkanoyl peroxide having a particular structure with a naphthalocyanine.

FIELD OF ART

The present invention relates to a novel derivative of naphthalocyaninecontaining a perfluoroalkyl group, and particularly to a process forpreparing such an industrially useful derivative of naphthalocyaninecontaining a perfluoroalkyl group and an optical recording mediumcapable of recording information using a focused beam of a semiconductorlaser.

BACKGROUND TECHNOLOGY

Cyanine compounds have hitherto been known to be used as absorbents forthe rays within the near infrared and infrared regions, but the cyaninecompounds are generally unstable to light and heat. On the other hand,since naphthalocyanine compounds are extremely stable to light, heat andhumidity and excellent in toughness, they attract attention to be usedas polymer materials for preparing films or thin membranes having highperformance characteristics by blending with various dyes, pigments,optical information recording media, photoelectric conversion media,electron photographic sensors and polymer materials.

However, naphthalocyanine compounds are generally scarcely soluble inorganic solvents and thus difficulties are encountered in forming filmsthereof by ordinary film forming processing. Accordingly, there is anearnest demand for a compound having excellent properties comparable tonaphthalocyanine compounds and capable of forming a film, and there isalso an earnest demand for the development of a process for preparingsuch a compound on an industrial scale.

Also already proposed and applied for practical use as optical recordingmedia are recording media each having an inorganic recording film layermade of a low melting point metal such as Te, Te alloys or Bi alloys.

However, production efficiency of such a recording medium having aninorganic recording film layer is low since the recording film layermust be formed by vacuum evaporation, or sputtering and there is aproblem in recording density since the thermal conductivity of therecording film layer is high. Furthermore, since a harmful metal is usedto prepare a recording medium having such an inorganic recording filmlayer, it is essential to overcome the problems concerning operationenvironment and waste water disposal.

In order to solve these problems, various proposals have been made touse phthalocyanine pigments which are known as blue to green pigmentsand excellent in stability as materials for optical recording media,specific examples being copper phthalocyanine, lead phthalocyanine,titanium phthalocyanine, vanadyl phthalocyanine and tin phthalocyanine(Unexamined Japanese Patent Publication Nos. 36490/1983 and 11292/1984).However, these pigments are inferior in matching with the semiconductorlasers, which are commonly used as the recording lasers at the presentday, having oscillation wavelengths at approximately 780 to 830 nm,since they have maximum absorption wavelengths in the vicinity of 700nm.

Under these circumstances, although there is proposed a process in whichthe absorption wavelengths are shifted to the long wavelenth region bymeans of processing with organic solvents or heating treatment, such aprocess has not yet been applied for practical use since these metalphthalocyanine pigments are scarcely soluble in organic solvents, inaddition to complicated processing steps, so that it is impossible toform a thin film on a substrate made of a thermoplastic resin substrate,such as polycarbonate by coating solutions thereof and it is inevitableto use vacuum evaporation coating or sputtering technique.

In order to solve various problems described above, an optical recordingmedium has been proposed, in which a soluble organic pigment is used toform a recording film layer on a substrate by coating. Morespecifically, developed and applied for practical use is an opticalrecording medium which is formed by spin coating an organic pigmentwhich has an absorption wavelength within the oscillation wavelengths ofsemiconductor lasers and is soluble in organic solvents, more specificexamples of such a pigment being dithiol-metal complexes, polymethinepigments, squaraine pigments, cyanine pigments and naphthoquinonepigments.

However, the optical recording media containing the aforementionedorganic pigments have disadvantages that they are poor in durability andweather-proof properties and low in reflectivity needed for reproducingthe informations. Also known in the art as pigments which are excellentin durability and weather-proof properties and have absorption peaksvicinal to 800 nm are naphthalocyanines having the tetraazaporphyrinskeletal structure similar to phthalocyanine pigments (Inorg. Chim.Acta., 44, L209 (1980); Zh. Obshch. Khim., 42(3), 696 (1972)). However,these known naphthalocyanines and metal salts thereof have adisadvantage that they are more scarcely soluble in general organicsolvents than the corresponding phthalocyanine compounds.

In recent years, various investigations have been made to improve thesolubility of naphthalocyanines and metal salts thereof in organicsolvents (Specification of U.S. Pat. No. 4,492,750, Specification ofU.S. Pat. No. 4,725,525, Unexamined Japanese Patent Publication No.25886/1986, J. Am. Chem. Soc., 106, 7404 (1984), Unexamined JapanesePatent Publication No. 177287/1986, Unexamined Japanese PatentPublication No. 177288/1986 and Unexamined Japanese Patent PublicationNo. 184565/1985), and it has been known that aromatic hydrocarbonsolvents and halogenated solvents may be used as the organic solventsfor dissolving these compounds. However, since the solubilities of thesecompounds, for example, in saturated hydrocarbon solvents and alcoholsolvents are extremely low, there arises a problem that a layerresisting to solvent must be formed on a polymethyl methacrylate orpolycarbonate substrate when a recording film layer is formed on such asubstrate.

Further known to improve the general solubilities of naphthalocyaninesis a method in which plural substituting groups having long chain alkylgroups are introduced. However, if the solubility is improved by such amethod, the melting point of the resultant product is lowered to inducea disadvantage that the recording film layer tends to melt when theoptical recording medium is subjected to reproduction for a long time aswell as during the recording step. Accordingly, there is a demand forthe development of a method for solubilizing the naphthalocyaninecompounds in saturated hydrocarbon solvents and alcohol solvents withoutlowering the melting points thereof.

In general, naphthalocyanines have a disadvantage that the once formedamorphous recording film is crystallized gradually under a hightemperature and high humidity condition to lose the recorded informationsince they have large planar χ-conjugated bonds to have extremeassociation force between individual molecules. Accordingly, therearises a problem that such crystallization must be suppressed.

Accordingly, an object of this invention is to provide a novelderivative of naphthalocyanine containing a perfluoroalkyl group, whichis excellent in weatherability, high in solubility in various organicsolvents and capable of forming a film, and to provide a process forpreparing the same.

Another object of this invention is to provide an industrially usefulprocess for preparing a derivative of naphthalocyanine containing aperfluoroalkyl group at high yield without using any special apparatusand reaction catalyst within a short time.

A further object of this invention is to provide an optical recordingmedium which has high sensitivity and durability including resistance toreproducing laser beam, resistance to environment and resistance tocrystallization.

DISCLOSURE OF THE INVENTION

According to the present invention, there is provided a derivative ofnaphthalocyanine containing a perfluoroalkyl group represented by thefollowing general formula (IV) of: ##STR1## (wherein M stands for H₂,copper, (R)₃ SiO--Si--OSi(R)₃ or [F(CF₂)_(n).sbsb.5 --(R)₂SiO--Si--OSi(R)₃ where R is an alkyl group having 1 to 10 carbon atoms;n₁, n₂, n₃ and n₄ each stand for an integer of from 0 to 2 and n₅ standsfor an integer of 1 to 10; n₁ +n₂ +n₃ +n₄ ≠ 0 when M is H₂, copper or(R)₃ SiO--Si--OSi(R)₃.

Meantime, both of the naphthalocyanine derivative containing aperfluoroalkyl group represented by the general formula (IV) wherein Mis H₂, and the naphthalocyanine derivative containing a perfluoroalkylgroup represented by the general formula (IV) wherein M are other thanH₂ are novel compounds.

The present invention further provides an optical recording mediumwherein a recording film layer mainly composed of a naphthalocyaninederivative containing a perfluoroalkyl group represented by the generalformula (IV) is formed on a substrate. It is preferred to use, as a maincomponent of the recording film layer, a single or mixed derivative ofnaphthalocyanine containing a perfluoroalkyl group and represented bythe aforementioned general formula (IV) wherein M is other than H₂ andcopper or a mixture of a single or mixed derivative of naphthalocyaninecontaining a perfluoroalkyl group and represented by the formula (IV)wherein M is other then H₂ and copper with a single or mixed derivativeof naphthalocyanine containing a perfluoroalkyl group represented by theaforementioned general formula (IV) wherein M is H₂ or copper.

The present invention further provides a process for preparing aderivative of naphthalocyanine containing a perfluoroalkyl grouprepresented by the aforementioned general formula (IV), comprisingreacting a naphthalocyanine with a perfluoroalkanoyl peroxiderepresented by the following general formula (III) of: ##STR2## (whereinn₅ stands for an integer of from 1 to 10.)

BEST EMBODIMENT FOR THE PRACTICE OF THE INVENTION

The present invention will be described more in detail in the followingdescription.

The derivatives of naphthalocyanine containing a perfluoroalkyl group,provided by this invention, is represented by the following generalformula (IV) of: ##STR3## In the formula, M stands for H₂, copper, (R)₃SiO--Si--OSi(R)₃ or [F(CF₂)_(n).sbsb.5 (R)₂ SiO--Si--OSi(R)₃ where R isan alkyl group having 1 to 10 carbon atoms; n₁, n₂, n₃ and n₄ each standfor an integer of from 0 to 2 and n₅ stands for an integer of 1 to 10;and n₁ +n₂ +n₃ +n₄ ≠0 when M is H₂, copper or (R)₃ SiO--Si--OSi(R)₃. Itbecomes difficult to prepare the derivatives if n₅ is more than 10,either one of n₁, n₂, n₃ and n₄ is more than 3 or R is an alkyl grouphaving more than 11 carbon atoms. Meantime, both of the naphthalocyaninederivative containing a perfluoroalkyl group represented by the generalformula (IV) wherein M is H₂ (hereinafter referred to asNaphthalocyanine Derivative A), and the naphthalocyanine derivativeseach containing a perfluoroalkyl group represented by the generalformula (IV) wherein M are other than H₂ (hereinafter referred to asNaphthalocyanine Derivatives B) are novel compounds.

It is preferred that the perfluoroalkylation ratio of the derivatives ofnaphthalocyanine each containing a perfluoroalkyl group, according tothis invention, ranges from 100 to 800% for the aforementionedNaphthalocyanine Derivative A and ranges from 100 to 900% for theaforementioned Naphthalocyanine Derivatives B. When one perfluoroalkylgroup is introduced per one naphthalocyanine molecule, it will bedescribed that the perfluoroalkylation ratio is 100%.

Preferable derivatives of naphthalocyanine each containing aperfluoroalkyl group and represented by the aforementioned generalformula (IV) include perfluoromethylated naphthalocyanine,perfluoroethylated naphthalocyanine, perfluoropropylatednaphthalocyanine, perfluorobutylated naphthalocyanine,perfluoropentylated naphthalocyanine, perfluorohexylatednaphthalocyanine, perfluoroheptylated naphthalocyanine,perfluorooctylated naphthalocyanine, perfluorononylatednaphthalocyanine, perfluorodecylated naphthalocyanine,tetraperfluoroethyl naphthalocyanine, tetraperfluoropropylnaphthalocyanine, perfluoromethylated copper naphthalocyanine,perfluoroethylated copper naphthalocyanine, perfluoropropylated coppernaphthalocyanine, perfluorobutylated copper naphthalocyanine,perfluoropentylated copper naphthalocyanine, perfluorohexylated coppernaphthalocyanine, perfluoroheptylated copper naphthalocyanine,perfluorooctylated copper naphthalocyanine, perfluorononylated coppernaphthalocyanine, perfluorodecylated copper naphthalocyanine,tetraperfluorobutyl copper naphthalocyanine, diperfluoropentyl coppernaphthalocyanine, diperfluorohexyl copper naphthalocyanine,diperfluoroheptyl copper naphthalocyanine, diperfluorooctyl coppernaphthalocyanine, diperfluorononyl copper naphthalocyanine,diperfluorodecyl copper naphthalocyanine, pentafluoropropyl coppernaphthalocyanine, perfluoropropyldihexylsiloxy-trihexylsiloxy-siliconnaphthalocyanine, perfluoropropylated(perfluoropropyl-dihexylsiloxy-trihexylsiloxy-silicon) naphthalocyanine,perfluoropropylated(perfluoropropyl-dihexylsiloxy-trihexylsiloxy-silicon) naphthalocyanine,perfluoropropylated(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)naphthalocyanine, perfluoropropylated(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)naphthalocyanine, perfluoropropylated(perfluoropropyldiethylsiloxy-triethylsiloxy-silicon) naphthalocyanine,tetraperfluoropropyl-bis(trimethylsiloxy) silicon naphthalocyanine,diperfluoropropyl-bis(trimethylsiloxy) silicon naphthalocyanine,diperfluorobutyl-bis(trimethylsiloxy) silicon naphthalocyanine,diperfluoropentyl-bis(trimethylsiloxy) silicon naphthalocyanine,diperfluorohexyl-bis(trimethylsiloxy) silicon naphthalocyanine,diperfluoroheptyl-bis(trimethylsiloxy) silicon naphthalocyanine,perfluorooctyl-bis(trimethylsiloxy) silicon naphthalocyanine,perfluorononyl-bis(trimethylsiloxy) silicon naphthalocyanine,perfluorodecyl-bis(trimethylsiloxy) silicon naphthalocyanine,tetraperfluoroethyl-bis(triethylsiloxy) silicon naphthalocyanine,tetraperfluoropropyl-bis(triethylsiloxy) silicon naphthalocyanine,perfluoropropyl-bis(triethylsiloxy) silicon naphthalocyanine,perfluorobutyl-bis(triethylsiloxy) silicon naphthalocyanine,perfluoropentyl-bis(triethylsiloxy) silicon naphthalocyanine,perfluorohexyl-bis(triethylsiloxy) silicon naphthalocyanine,perfluoroheptyl-bis(triethylsiloxy) silicon naphthalocyanine,diperfluoroethyl-bis(tripropylsiloxy) silicon naphthalocyanine,perfluoropropyl-bis(tripropylsiloxy) silicon naphthalocyanine,diperfluoropropyl-bis(tripropylsiloxy) silicon naphthalocyanine,triperfluoropropyl-bis(tripropylsiloxy) silicon naphthalocyanine,perfluorobutyl-bis(tripropylsiloxy) silicon naphthalocyanine,perfluoroethyl-bis(tributylsiloxy) silicon naphthalocyanine,diperfluoroethyl-bis(tributylsiloxy) silicon naphthalocyanine,tetraperfluoroethyl-bis(tributylsiloxy) silicon naphthalocyanine,perfluoropropyl-bis(tributylsiloxy) silicon naphthalocyanine,diperfluoropropyl-bis(tributylsiloxy) silicon naphthalocyanine,tetraperfluoropropyl-bis(tributylsiloxy) silicon naphthalocyanine,perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon naphthalocyanine,diperfluoropropyl(perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon)naphthalocyanine,triperfluoropropyl(perfluoro-propyldipropylsiloxy-tripropylsiloxy-silicon)naphthalocyanine,diperfluoropropyl(perfluoropropyl-diethylsiloxy-triethylsiloxy-silicon)naphthalocyanine,perfluoropropyl(perfluoropropyldiethylsiloxy-triethylsiloxy-silicon)naphthalocyanine, diperfluoroethyl-bis(trihexylsiloxy) siliconnaphthalocyanine, triperfluoroethyl-bis(trihexylsiloxy) siliconnaphthalocyanine, perfluoropropyl-bis(trihexylsiloxy) siliconnaphthalocyanine, diperfluoropropyl-bis(trihexylsiloxy) siliconnaphthalocyanine, tetraperfluoropropyl-bis(trihexylsiloxy) siliconnaphthalocyanine, perfluorohexyl-bis(trihexylsiloxy) siliconnaphthalocyanine, perfluoromethyl-bis(trihexylsiloxy) siliconnaphthalocyanine, perfluoroethyl-bis(trihexylsiloxy) siliconnaphthalocyanine, perfluoropropyl-bis(trihexylsiloxy) siliconnaphthalocyanine, perfluorobutyl-bis(trihexylsiloxy) siliconnaphthalocyanine, perfluoropentyl-bis(trihexylsiloxy) siliconnaphthalocyanine and perfluorohexyl-bis(trihexylsiloxy) siliconnaphthalocyanine. Meanwhile, in the illustrated derivatives ofnaphthalocyanine each containing a perfluoroalkyl group,"perfluoroalkylation" such as "perfluoropropylation" means that aperfluoroalkyl group represented by [(CF₂)n₄.sbsb.5 F]_(n).sbsb.4(wherein n₄ and n₅ are the same as n₄ and n5 defined in theaforementioned general formula (IV) is coupled to at least one of sixpositions of the naphthalene ring present in the aforementioned generalformula (IV) at which such a group may be coupled. However, when M inthe aforementioned general formula (II) is [F(CF₂ --_(n).sbsb.5 (R)₂SiO--Si--OSi(R)₃,it is not always essential that a perfluoroalkyl groupis coupled to the naphthalene ring since a perfluoroalkyl group isalready present in M.

The process for preparing a derivative of naphthalocyanine representedby the aforementioned general formula (IV), according to this invention,is characterized in that a particular perfluoroalkanoyl peroxide isreacted with any of naphthalocyanines.

The perfluoroalkanoyl peroxides, which are used as a feed component inthe process of this invention, may be represented by the followinggeneral formula (III) of: ##STR4## In the formula set forth above, n₅stands for an integer of from 1 to 10. n₅ must be within the range asdefined above, since the solubility of the peroxides in a solvent islowered if n₅ exceeds 10 so that handling thereof in reaction becomesdifficult. Specific examples of the perfluoroalkanoyl peroxidesrepresented by the aforementioned general formula (III) includebis(perfluoroacetyl) peroxide, bis(perfluoropropionyl) peroxide,bis(perfluorobutyryl) peroxide, bis(perfluoropentanoyl) peroxide,bis(perfluorohexanoyl) peroxide, bis(perfluoroheptanoyl) peroxide,bis(perfluorooctanoyl) peroxide, bis(perfluoropelargonyl) peroxide,bis(perfluorodecanoyl) peroxide and bis(perfluoroundecanoyl) peroxide.

Specific examples of the naphthalocyanines which may be reacted with theaforementioned perfluoroalkanoyl peroxides in the process of thisinvention include naphthalocyanine, copper naphthalocyanines, andsilicon naphthalocyanines represented by the following general formula(VII) of: ##STR5## (wherein R stands for an alkyl group having 1 to 10carbon atoms.)

Specific examples of the silicon naphthalocyaines includebis(trimethylsiloxy) silicon naphthalocyanine, bis(triethylsiloxy)silicon naphthalocyanine, bis(tripropylsiloxy) silicon naphthalocyanine,bis(tributylsiloxy) silicon naphthalocyanine, bis(tripentylsiloxy)silicon naphthalocyanine, bis(trihexylsiloxy) silicon naphthalocyanine,bis(triheptylsiloxy) silicon naphthalocyanine, bis(trioctylsiloxy)silicon naphthalocyanine, bis(trinonylsiloxy) silicon naphthalocyanineand bis(tridecylsiloxy) silicon naphthalocyanine.

It is preferred that the naphthalocyanines and the perfluoroalkanoylperoxides are charged in a molar ratio of from 1:0.2 to 20, particularly1:0.5 to 10. If the molar ratio of charged perfluoroalkanoyl peroxide isless than 0.2, the yield of the produced derivative of naphthalocyaninecontaining an alkyl group is lowered and the ratio of perfluoroalkylgroup introduced in the produced naphthalocyanine is reduced, whereas itis not preferable that the ratio of charged perfluoroalkanoyl peroxideexceeds 20, since sole decomposition of perfluoroalkanoyl peroxidebecomes predominant to make the process impertinent for industrialpreparation process.

The reaction between the perfluoroalkanoyl peroxides and thenaphthalocyanines may proceed under atmospheric pressure, preferably ata reaction temperature of from -20° to 150° C., particularly preferablyfrom 0° to 100° C., for 0.5 to 20 hours, whereby derivatives ofnaphthalocyanine each containing an introduced perfluoroalkyl group,such as CF₃ --, F(CF₂ --₂, F(CF₂ --₃, F(CF₂ --₄, F(CF₂ --₅, F(CF₂ --₆,F(CF₂ --₇, F(CF₂ --₈, F(CF₂ --₉, and F(CF₂ --₁₀, , may be prepared. Thereaction time becomes too long if the reaction temperature is lower than-20° C., whereas the pressure during reaction becomes disadvantageouslyhigh to arise difficulty in reaction operation if the reactiontemperature is higher than 150° C.

When the perfluoroalkanoyl peroxides are reacted with thenaphthalocyanines according to this invention, the reaction may proceedin the presence of a solvent, for example a halogenated aliphaticcompound, for easy handling of the perfuloroalkanoyl peroxide. The mostpreferable halogenated aliphatic solvent from the industrial point ofview is 1,1,2-trichloro-1,2,2-trifluoroethane.

The reaction products prepared by this invention may be purified throughknown processes including column chromatography.

The optical recording medium of this invention is characterized in thatthe main component of the recording film layer formed on a substrate isany of the derivatives of naphthalocyaines (hereinafter referred to asNaphthalocyanine Derivatives C) represented by the aforementionedgeneral formula (IV), more preferably the main component is selectedfrom the derivatives of naphthalocyanines (hereinafter referred to asNaphthalocyanine Derivatives D) included in the NaphthalocyanineDerivatives C wherein M in the formula is other than H₂ and copper, or amixture of the Naphthalocyanine Derivatives D with any of thederivatives of naphthalocyanine (hereinafter referred to asNaphthalocyanine Derivatives E) wherein M in the formula is H₂ orcopper.

Since each of the derivatives of naphthalocyanine according to thisinvention has perfluoroalkyl group, the association power betweenindividual molecules is lowered, as compared to the unsubstitutednaphthalocyanine, so that the solubility thereof in a solvent isremarkably improved. Meanwhile, although the solubility may be improvedby the introduction of an alkyl group into naphthalocyanine, improvementin solubility is appreciably improved by the introduction of aperfluoroalkyl group when the product prepared by the introduction of aperfluoroalkyl group having a certain number of carbon atom is comparedto the product prepared by the introduction of an alkyl group having thesame number of carbon atoms. In general, the melting points ofnaphthalocyanines are lowered gradually with the increase in number ofthe introduced substituting groups and as described above, since theproducts prepared by the introduction of perfluoroalkyl groups have thesolubilities equivalent to or higher than the solubilities of theproducts prepared by the introduction of alkyl groups even when thenumber of introduced substituting groups is smaller, the aforementionedderivatives of naphthalocyanine are compounds which are improved insolubility and suppressed in attendant lowering of melting point.Particularly, since the aforementioned Naphthalocyanine Derivatives Dare introduced with perfluoroalkyl groups which are intensive in stericrepelling force, they are particularly preferable for use as the maincomponent in the recording film layer without appreciable reduction inreflectivity due to intermolecular association. On the other hand, theaforementioned Naphthalocyanine Derivatives E have the tendency that thereflectivities and the absorbancies (100 -- Reflectivity -- PercentTransmission) thereof are lower as compared to those of theaforementioned Naphthalocyanine Derivatives D, so that the stabilityagainst the reproducing laser beam can be improved by using a mixture ofthe Naphthalocyanine Derivatives D with the Naphthalocyanine DerivativesE as the main component for forming the recording film layer by theutilization of the aformentioned characteristics. It is preferable thatthe mixing ratio of the aforementioned Naphthalocyanine Derivatives Dand the Naphthalocyanine Derivatives E ranges within 10:1 to 5 byweight, particularly preferably within 10:1 to 3 by weight. Meantime,preferable examples of the aforementioned derivatives ofnaphthalocyanine include those specifically represented by the generalformula (IV) set forth above, and in principle they may be used singlyor in the form of a mixture.

In order to form a recording film layer on a substrate to prepare anoptical recording medium in the present invention, the aforementionedderivatives of naphthalocyanine may be dissolved, for example, in anappropriate organic solvent and coated by spray coating, spin coating orother processes to be carried on the substrate. Suitable materials forthe substrate include thermoplastic resins such as polyvinyl chlorideresins, acrylic resins, polyolefin resins, polycarbonate resin andpolyvinyl acetal resin; thermosetting resins such as epoxy resins,unsaturated polyester resins and vinyl ester resins; and glass andmetals. For instance, when recording and reproduction are effected byirradiating a laser beam from the substrate side, the substrate must betransparent in the wavelength range of the used laser beam. Thesubstrate may have a construction composed of a flat plate molded fromthe aforementioned materials and a photocured resin layer laminated onthe flat plate, the photocured resin layer having a surface on which aguide track pattern is transferred.

For instance, when the material for the substrate is a thermoplasticresin, a solvent which does not damage the pre-groove or pre-pit formedin the substrate may be used for forming the aforementioned recordingfilm layer, the examples being saturated hydrocarbon solvents such aspentane, hexane, heptane, octane, nonane, decane, cyclopentane,cyclohexane and cycloheptane; alcohol solvents such as methanol,ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol andt-butyl alcohol; benzene, toluene, xylene, chlorobenzene,1-chloronaphthalene, methylene chloride, chloroform, carbontetrachloride, trichloroethane, diethyl ether, ethyleneglycol dimethylether, diethyleneglycol monomethyl ether, diethyleneglycol dimethylether, ethylbenzene, methyl ethyl ketone, acetone, methyl propyl ketone,cyclopentanone, cyclohexanone, acetone alcohol, diacetone alcohol,diisobutyl ketone, propylene oxide, furan, 1,3-dioxolan, acetate,dimethoxymethane, dimethoxypropane, diethoxymethane,1,2-dimethoxypropane, 2,2-dimethoxypropane. 2-pentanone, 3-pentanone,1,2-butylene oxide, n-butyl-2,3-epoxy propyl ether, carbon disulfide,diisopropyl ether, nitromethane, acetonitrile, 1,3-dicyanopropane,dioxane and ethyl acetate. These solvents may be used singly or in theform of a mixture.

The aforementioned recording film layer may be formed by applying eachof the aforementioned derivatives of naphthalocyanine used as the maincomponent of the recording film layer in the laminated structure or inthe single layer structure. The aforementioned derivatives ofnaphthalocyanine may be used singly or in the form of a mixture, andeach of them may be laminated or they may be mixed together and thenused to form a single layer structure. The film thickness of theaforementioned recording film layer ranges preferably from 50 to 10000Å, particularly preferably from 100 to 5000 Å.

A reflected light may be used for the optical reproduction of therecorded image stored in the aforementioned recording film layer. Inorder to raise the contrast in this step, a metal layer having a highreflectivity may be provided, if necessary, on the surface of therecording film layer opposite to the substrate when the image is writtenin and read out from the substrate side; or a metal layer having a highreflectivity may be provided between the substrate and the recordingfilm layer when the image is written in and read out from the sideopposite to the substrate, namely from the recording film layer side. Asthe metal having a high reflectivity, Al, Cr, Au, Pt and Sn may be used.Such a layer may be formed by the known thin film forming processes,such as vacuum evaporation, sputtering or plasma deposition, and thethickness thereof ranges preferably from 100 to 10000 Å.

In order to improve the smoothness of the surface of the aforementionedsubstrate, a uniform membrane of an organic polymer compound may beprovided over the substrate. Commercially available polymers, such aspolyesters or polyvinyl chloride, may be used as the organic polymercompound.

Furthermore, in order to improve the stability and protection propertiesof the recording film layer and further to lower the surfacereflectivity to increase the sensitivity, a protection layer may beprovided as an outermost ply of the recording film layer. Materials forforming such a protection layer include polyvinilidene chloride,polyvinyl chloride, copolymers of vinylidene chloride and acrylonitrile,polyvinyl acetate, polyimide, polymethyl methacrylate, polystyrene,polyisoprene, polybutadiene, polyurethane, polyvinyl butyral,fluorinated rubbers, polyesters, epoxy resins, silicone resins andcellulose acetate, these materials being used singly or in the form of amixture. With the aim to reinforce the properties of such a protectionlayer, silicone oil, an antistatic agent or a cross-linking agent may bepresent in the layer, or plural protection layers may be provided. Sucha protection layer may be formed, for example, by dissolving a materialfor forming the protection layer followed by coating, or by laminating athin film for forming the protection layer. The thickness of theprotection layer ranges preferably from 0.1 to 10 μm, particularlypreferably from 0.1 to 2 μm.

The derivatives of naphthalocyanine each containing a perfluoroalkylgroup, according to this invention, are novel compounds and are solublein various organic solvents, so that they are useful as opticalinformation recording media, photo-electric convertors, photosensitivematerials for electron photography or polymer materials for blendingwith other polymers to form films or thin membranes having highperformance characteristics.

Since particular perfluoroalkanoyl peroxides are used in the process ofthis invention, perfluoroalkyl groups can be directly and easilyintroduced into naphthalocyanines within a short period at high yield.In addition, since no reaction catalyst and no special device are used,it is extremely useful from the industrial standpoint of view.

Furthermore, since the optical recording medium according to thisinvention is formed by using, as the main component for forming therecording film layer, a compound excellent in resistance to laser beamused for reproduction, resistance to environment and resistance tocrystallization and improved in solubility, it is high in sensitivityand excellent in durability and thus extremely useful when used, forexample, as an optical disc, optical card or optical floppy.

EXAMPLES:

The present invention will be described more in detail by referring toExamples and Test Examples thereof in the following description, but itis to be noted here that the present invention is not restrictedthereby.

EXAMPLE 1

0.5 g (0.7 mmol) of naphthalocyanine was added to and mixed with 10 g of1,1,2-trichloro-1,2,2-trifluoroethane, to which added was 20 g of asolution of 1,1,2-trichloro-1,2,2-trifluoroethane containing 3.5 mmol ofbis(perfluorobutyryl) peroxide to proceed the reaction at 40° C. for 5hours. After the completion of reaction, 50 ml of chloroform was addedto the reaction mixture, which was then filtered to remove unreactedmaterials. Then, the obtained chloroform layer was dried by usingmagnesium sulfate, and the product was purified through columnchromatography. As a result, tetraperfluoropropyl naphthalocyaninerepresented by the following structural formula was obtained at a yieldof 72%. ##STR6## Meanwhile, the number of perfluoropropyl groupsintroduced in naphthalocyanine, i.e. the perfluoropropylation ratio, wasdetermined by ¹⁹ F--NMR while using benzotrifluoride as an internalstandard indicator to find that the perfluoropropylation ratio was 400%,namely four perfluoropropyl groups were introduced per one molecule. TheUV spectrum (Solvent used in Measurement: Chloroform), IR spectrum and¹⁹ F-NMR spectrum of the thus prepared perfluoropropylatednaphtalocyanine are set forth below.

UV (nm): 261, 711.0, 729.0, 762.5.

IR (cm ⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₀₂ H) δ: -8 to -10 (CF₃), -20 to -38(CF₂), -46 to -58 (CF₂).

EXAMPLE 2

Similar reaction and analyses were repeated as in Example 1, except thatthe charged quantity of bis(perfluorobutyryl) peroxide was changed to2.8 mmol, to prepare perfluoropropylated naphthalocyanine at a yield of69%. Meanwhile, the perfluoropropylation ratio was determined similarlyto Example 1 to find that the perfluoropropylation ratio was 300%. Theresults of analyses of the thus prepared perfluoropropylatednaphthalocyanine are set forth below.

UV (nm): 260, 592.5, 649.5, 669.0, 726.5.

IR (cm ⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -8 to -10 (CF₃), -20 to -38(CF₂), -46 to -58 (CF₂).

EXAMPLE 3

Similar reaction and analyses were repeated as in Example 1, except thatbis(perfluoropropionyl) peroxide was used in place ofbis(perfluorobutyryl) peroxide, to prepare perfluoroethylatednaphthalocyanine at a yield of 70%. Meanwhile, the perfluoroethylationratio was determined similarly to Example 1 to find that theperfluoroethylation ratio was 400%. The results of analyses of the thusprepared perfluoroethylated naphthalocyanine are set forth below.

UV (nm): 670.0, 735.5.

IR (cm ⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -8 to -10 (CF₃), -43 to -56(CF₂).

EXAMPLE 4

Similar reaction and analyses were repeated as in Example 1, except thatbis(perfluoroheptanoyl) peroxide was used in place ofbis(perfluorobutyryl) peroxide, to prepare perfluorohexylatednaphthalocyanine at a yield of 65%. Meanwhile, the perfluorohexylationratio was determined similarly to Example 1 to find that theperfluorohexylation ratio was 400%.

The results of analyses of the thus prepared perfluorohexylatednaphthalocyanine are set forth below.

UV (nm): 260, 590.0, 670.8, 735.5.

IR (cm ⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -5 to -10 (3F), -30.1 to -51.5(10F).

EXAMPLE 5

Similar reaction and analyses were repeated as in Example 1, except thatbis(perfluorooctanoyl) peroxide was used in place ofbis(perfluorobutyryl) peroxide, to prepare perfluoroheptylatednaphthalocyanine at a yield of 65%. Meanwhile, the perfluoroheptylationratio was determined similarly to Example 1 to find that theperfluoroheptylation ratio was 400%.

The results of analyses of the thus prepared perfluoroheptylatednaphthalocyanine are set forth below.

UV (nm): 261, 670.8, 735.5.

IR (cm⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ:

-5 to -10(3F), -30.1 to -51.5(12F).

Example 6

Similar reaction and analyses were repeated as in Example 1, except that0.2 g (0.26 mmol) of copper naphthalocyanine was used in place ofnaphthalocyanine and that the charged quantity of bis(perfluorobutyryl)peroxide was changed to 2.06 mmol, to prepare perfluoropropylated coppernaphthalocyanine at a yield of 36%. Meanwhile, the perfluoropropylationratio was determined similarly to Example 1 to find that theperfluoropropylation ratio was 490%. The results of analyses of the thusprepared perfluoropropylated copper naphthalocyanine are set forthbelow. ##STR7##

UV (nm): 668.5, 736.5.

IR (cm ⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -8 to -10 (CF₃), -20 to -38(CF₂). -46 to -58 (CF₂).

EXAMPLE 7

Similar reaction and analyses were repeated as in Example 1, except that0.5 g (0.37 mmol) of bis(trihexylsiloxy) silicon naphthalocyanine wasused in place of naphthalocyanine and that the charged quantity ofbis(perfluorobutyryl) peroxide was changed to 0.37 mmol, to prepare(perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon) naphthalocyaninehaving the structure as set forth below at a yield of 46%. ##STR8##Meanwhile, the perfluoropropylation ratio was determined similarly toExample 1 to find that the perfluoropropylation ratio was 100%. Theresults of analyses and the melting point (mp) of the thus preparedperfluoropropyldihexylsiloxy-trihexylsiloxy-silicon naphthalocyanine areset forth below.

UV (nm): 779, 761

IR (cm⁻¹): 1340 (CF₃ ), 1225 (CF₂).

mp: 226° C. to 228° C. ¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -2.8(CF₃), -18.0 (CF₂), -45.7 (CF₂).

EXAMPLE 8

Similar reaction and analyses were repeated as in Example 1, except that0.5 g (0.37 mmol) of bis(trihexylsiloxy) silicon naphthalocyanine wasused in place of naphthalocyanine and that the charged quantity ofbis(perfluorobutyryl) peroxide was changed to 1.42 mmol, to preparediperfluoropropyl(perfluoropropyldihexhlsiloxy-trihexylsiloxy-silicon)naphthalocyanine having the structure as set forth below at a yield of46%. ##STR9## Meanwhile, the perfluoropropylation ratio was determinedsimilarly to Example 1 to find that the perfluoropropylation ratio was300%. The results of analyses of the thus prepareddiperfluoropropyl(perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon)naphthalocyanine are set forth below.

UV (nm): 771.

IR (cm⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -2.5 to -5.5 (CF₃), -17.0 to-21.5 (CF2), -44.5 to -46.8 (CF₂).

EXAMPLE 9

Similar reaction and analyses were repeated as in Example 1, except that0.5 g (0.46 mmol) of bis(tripropylsiloxy) silicon naphthalocyanine wasused in place of naphthalocyanine and that the charged quantity ofbis(perfluorobutyryl) peroxide was changed to 0.92 mmol, to preparediperfluoropropyl(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)naphthalocyanine having the structure as set forth below at a yield of13%. ##STR10## Meanwhile, the perfluoropropylation ratio was determinedsimilarly to Example 1 to find that the perfluoropropylation ratio was300%. The results of analyses of the thus prepareddiperfluoropropyl(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)naphthalocyanine are set forth below.

UV (nm): 764, 675.

IR (cm⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -2.8 to -6.0 (CF₃), -17.2 to-19.0 (CF₂), -44.0 to -47.9 (CF₂).

EXAMPLE 10

Similar reaction and analyses were repeated as in Example 1, except that0.5 g (0.46 mmol) of bis(tripropylsiloxy) silicon naphthalocyanine wasused in place of naphthalocyanine and that the charged quantity ofbis(perfluorobutyryl) peroxide was changed to 1.84 mmol, to preparetriperfluoropropyl(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)naphthalocyanine having the structure as set forth below at a yield of50%. ##STR11## Meanwhile, the perfluoropropylation ratio was determinedsimilarly to Example 1 to find that the perfluoropropylation ratio was400%. The results of analyses of the thus preparedtriperfluoropropyl(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)naphthalocyanine are set forth below.

UV (nm): 773, 668, 613.

IR (cm⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -2.8 to -6.5 (CF₃), -17.5 to-22.0 (CF₂), -45.0 to -52.0 (CF₂).

EXAMPLE 11

Similar reaction and analyses were repeated as in Example 1, except that0.5 g (0.50 mmol) of bis(triethylsiloxy)silicon naphthalocyanine wasused in place of naphthalocyanine and that the charged quantity ofbis(perfluorobutyryl) peroxide was changed to 1.00 mmol, to preparediperfluoropropyl(perfluoropropyldiethylsiloxy-triethylsiloxy-silicon)naphthalocyanine having the structure as set forth below at a yield of13%. ##STR12## Meanwhile, the perfluoropropylation ratio was determinedsimilarly to Example 1 to find that the perfluoropropylation ratio was300%. The results of analyses of the thus prepareddiperfluoropropyl(perfluoropropyldietylsiloxy-triethylsiloxy-silicon)naphthalocyanine are set forth below.

UV (nm): 767, 676.

IR (cm⁻¹): 1340 (CF₃), 1225 (CF₂).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -2.8 to -3.6 (CF₃), -18.2 to-20.5 (CF2), -45.1 to -47.3 (CF₂).

EXAMPLE 12

0.5 g (0.37 mmol) of bis(trihexylsiloxy)silicon naphthalocyanine wasadded to and mixed with 20 ml of chloroform, to which added was 3.2 g ofa solution of 1,1,2-trichloro-1,2,2-trifluoroethane containing 0.16 g(0.37 mmol) of bis(perfluorobutyryl) peroxide to proceed the reaction at40° C. for 5 hours. After the completion of reaction, the reactionmixture was rinsed with a 0.5 wt % aqueous solution of sodium hydroxideand saturated aqueous saline. Then, the thus obtained chloroform layerwas dried with magnesium sulfate, and the product was purified throughcolumn chromatography and further recrystallized by using a mixedsolution of hexane ethanol. As a result,perfluoropropyl-bis(trihexylsiloxy) silicon naphthalocyanine representedby the following structural formula was prepared at a yield of 43%.##STR13##

Meanwhile, the number of perfluoroalkyl groups introduced in thenaphthalocyanine was determined by ¹⁹ F--NMR while usingo-chlorobenzotrifluoride as an internal standard liquid to find that thenumber of perfluoroalkyl groups was 1. The UV (Solvent Used inMeasurement: Chloroform), IR, ¹ H--NMR, ¹⁹ F--NMR and the melting pointof the thus prepared perfluoropropyl-bis(trihexylsiloxy) siliconnaphtalocyanine are shown below.

UV (nm): 781, 766.

IR (cm⁻¹) 1350 (CF₃), 1225 (CF₂).

¹ H--NMR (CDCl₃)δ: 10.55 to 9.95 (m, 7H) 9.15 to 8.45 (m, 8H) 7.95 (b,8H), 1.00 to 0.00 (m, 54H) -0.95 (b, 12H), -1.90 to -2.25 (m, 12H).

¹⁹ F--NMR (CDCl₃, external, CF₃ CO₂ H) δ: -2.8 (CF₃), -18.0 (CF₂), -45.7(CF₂).

Melting Point (°C.): 226 to 228.

TEST EXAMPLE 1

Perfluoroalkylated naphthalocyanines prepared by Examples 1 to 12 weremixed with respective solvents as set forth in Table 1 to investigatethe solubilities thereof. The solubility of naphthalocyanine wasinvestigated as Comparative Example 1. The results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Example No./Solvent                                                                        a     b     c   d   e   f   g   h   i   j                        ______________________________________                                        Example 1    ⊚                                                                    ⊚                                                                    ⊚                                                                  X   ◯                                                                     Δ                                                                           ⊚                                                                  ⊚                                                                  Δ                                                                           X                        Example 2    ⊚                                                                    ⊚                                                                    ⊚                                                                  X   ◯                                                                     Δ                                                                           ⊚                                                                  ⊚                                                                  Δ                                                                           X                        Example 3    ⊚                                                                    ⊚                                                                    ⊚                                                                  X   ◯                                                                     Δ                                                                           ⊚                                                                  ⊚                                                                  Δ                                                                           X                        Example 4    ⊚                                                                    ⊚                                                                    ⊚                                                                  X   ◯                                                                     X   ⊚                                                                  ⊚                                                                  X   X                        Example 5    ⊚                                                                    ⊚                                                                    ⊚                                                                  X   ◯                                                                     X   ⊚                                                                  ⊚                                                                  X   X                        Example 6    ⊚                                                                    ⊚                                                                    ⊚                                                                  X   ◯                                                                     X   ⊚                                                                  ⊚                                                                  X   X                        Example 7    ⊚                                                                    ⊚                                                                    ⊚                                                                  X   ◯                                                                     Δ                                                                           ⊚                                                                  ⊚                                                                  Δ                                                                           ◯            Example 8    ⊚                                                                    ⊚                                                                    ⊚                                                                  X   ◯                                                                     Δ                                                                           ⊚                                                                  ⊚                                                                  ◯                                                                     ◯            Example 9    ⊚                                                                    ⊚                                                                    ⊚                                                                  ◯                                                                     ⊚                                                                  ⊚                                                                  ⊚                                                                  ⊚                                                                  ◯                                                                     ◯            Example 10   ⊚                                                                    ⊚                                                                    ⊚                                                                  ◯                                                                     ⊚                                                                  ⊚                                                                  ⊚                                                                  ⊚                                                                  ◯                                                                     ◯            Example 11   ⊚                                                                    ⊚                                                                    ⊚                                                                  ◯                                                                     ⊚                                                                  ⊚                                                                  ⊚                                                                  ⊚                                                                  ◯                                                                     ◯            Example 12   ⊚                                                                    ⊚                                                                    ⊚                                                                  X   ◯                                                                     ◯                                                                     ⊚                                                                  ⊚                                                                  Δ                                                                           Δ                  Comparative  X     X     X   X   X   X   X   X   X   X                        Example 1                                                                     ______________________________________                                         The marks in the Table indicate the following meanings.                       a: chloroform, b: Diethyl Ether, c: Tetrahydrofuran                           d: Methanol, e: Benzene, f: Hexane, g: Ethyl Acetate                          h: Acetone, i: Dimethylformamide, j: Ethanol                                  ⊚: Easily Soluble, ◯: Soluble Δ: Scarcel     Soluble                                                                       X: Insoluble                                                             

As seen from the results set forth in Table 1, the derivatives ofnaphthalocyanine each containing a perfluoroalkyl group, according tothis invention, are soluble in various solvents and thus useful forforming a processed film.

EXAMPLES 13 to 15

Similarly to the preceding Examples,triperfluoropropyl-bis(tripropylsiloxy) silicon naphthalocyanine(Example 13), diperfluoropropyl-bis(tributylsiloxy) siliconnaphthalocyanine (Example 14) and diperfluoroethyl-bis(tributylsiloxy)silicon naphthalocyanine (Example 15) were synthesized and subjected tovarious analyses to identify the structures thereof.

EXAMPLE 16

On each of the substrates having different compositions as set forth inTable 2 and each having a thickness of 1.2 mm and a diameter of 130 mm,coated by spin coating process was a solution consisting of 1 part byweight of each of the derivatives of naphthalocyanine as set forth inTable 2 and 99 parts by weight of a solvent, whereby each of recordingfilm layers was formed. The thickness of the thus formed recording filmlayer was measured by "Dektak 3030" (Trade Name) produced by Sloan Co.The thus prepared optical recording medium was placed on a turn tableand rotated at 1800 rpm, and pulse signals of 3.7 MHz were recordedthereon within the radius range of from 40 to 60 mm by using an opticalhead provided with a semiconductor laser having an oscillationwavelength of 830 nm with an output of 6 mW on the surface of thesubstrate so that the laser beam is focused through the substrate on therecording film layer from the substrate side. Then, using a similardevice, the output of a semiconductor laser on the surface of thesubstrate was set to 1.0 mW to reproduce the recorded signals, and theCN ratio (carrier-noise ratio) at the reproduction step was appraised.Furthermore, each of the prepared optical recording media was allowed tostand under a high temperature and high humidity condition (80° C., 90%RH) for 3000 hours, and then the CN ratio was measured. The results areshown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Derivative of         Thickness                                                                           Initial                                                                            CN Ratio after the                           Naphthalocyanine      of film                                                                             CN Ratio                                                                           Lapse of 3000 hours                          (ratio by weight)                                                                      Substrate*                                                                          Solvent                                                                              (Å)                                                                             (dB) (dB)                                         __________________________________________________________________________    Example 12                                                                             PC    Cyclohexane                                                                          700   62   62                                           Example 8                                                                              PC    Cyclohexane                                                                          790   59   60                                           Example 9                                                                              PC    Cyclohexane                                                                          760   62   60                                           Example 10                                                                             PC    Cyclohexane                                                                          800   58   58                                           Example 11                                                                             PC    Cyclohexane                                                                          830   57   59                                           Example 13                                                                             PMMA2P                                                                              Toluene                                                                              900   59   59                                           Exampl4 14                                                                             PMMA2P                                                                              Toluene                                                                              920   62   60                                           Example 15                                                                             PC    Ethanol                                                                              680   60   61                                           Example 12                                                                             PC    Ethanol                                                                              700   61   61                                           Example 8                                                                              PMMA  Ethanol                                                                              720   58   58                                           Example 9                                                                              PMMA2P                                                                              Chloroform                                                                           910   57   58                                           Example 11                                                                             PMMA2P                                                                              Chloroform                                                                           890   59   57                                           Ex. 8:Ex. 1 (7:3)                                                                      PC    Cyclohexane                                                                          1010  59   61                                           Ex. 15:Ex. 1 (9:2)                                                                     PC    Cyclohexane                                                                          970   58   60                                           Ex. 15:Ex. 1 (8:2)                                                                     PC    Cyclohexane                                                                          950   61   60                                           Ex. 15:Ex. 1 (7:3)                                                                     PC    Cyclohexane                                                                          990   62   61                                           __________________________________________________________________________     *PC: Polycarbonate Substrate, PMMA: Polymethyl Methacrylate Substrate         PMMA2P: Polymethyl Methacrylate 2P Substrate                             

As will be seen from the results shown in Table 2, the derivatives ofnaphthalocyanine used to form optical recording media, according to thisinvention, form recording film layers having superior recording andreproducing properties on various substrates, such as polycarbonatesubstrate, and that the thus formed recording film layers are excellentin amorphous film retention capability under an acceleratedenvironmental test condition.

COMPARATIVE EXAMPLE 2

A recording film layer was formed by coating, by the spin coatingprocess similar to Example 16, a solution consisting of 1 part by weightof a compound represented by the following structural formula and 99parts by weight of toluene on a polymethyl methacrylate 2P substratehaving a thickness of 1.2 mm and a diameter of 130 mm. The thickness ofthe thus formed recording film layer was 1000 Å. Similarly to Example16, recording and reproduction were effected using the thus preparedrecording medium to find that the CN ratio was 39 dB and that therecording and read-out of the signals were not so satisfactory. Inaddition, the recording film layer was crystallized to formmicrocrystals to lose its reproduction capability after it was retainedunder a high temperature and high humidity condition (80° C., 90% RH)for 500 hours. ##STR14##

COMPARATIVE EXAMPLE 3

A recording film layer was formed by coating, by the spin coatingprocess similar to Example 16, a solution consisting of 1 part by weightof a cyanine pigment NK-2905 (produced by Nippon Kanko ShikisoKenkyusho) and 99 parts by weight of dichloroethane on a polymethylmethacrylate 2P substrate having a thickness of 1.2 mm and a diameter of130 mm. The thickness of the thus formed recording film layer was 700 Å.The thus prepared recording medium was allowed to stand for 3000 hoursunder a high temperature and high humidity condition (80° C., 90% RH),and then the reflectivity thereof was measured to find that thereflectivity was abruptly lowered after the lapse of about 500 hours toshow the lack of satisfactory durability. The CN ratio retentionproperties under an accelerated environmental condition was appraised bya similar procedure as described in Example 16 to find that the CN ratiowas lowered to 70% of the initial CN ratio.

EXAMPLE 17

Durability to a reproducing laser beam (830 nm) of each of the opticalrecording media prepared in Example 16 was appraised. The appraisal testwas conducted by measuring the CN ratio after repeated reproduction of10⁶ times while setting the output of the used reproducing laser beam to1.0 mW, 1.4 mW and 1.6 mW. The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        Derivative          CN Ratio after Repeated                                   of Naphtha-                                                                              Initial  Reproduction of 10.sup.6 Times                            locyanine  CN Ratio (dB)                                                      (ratio by wt.)                                                                           (dB)     1.0 mW    1.4 mW 1.6 mW                                   ______________________________________                                        Example 12 62       62        62     52                                       Example 8  59       59        58     50                                       Example 9  62       62        60     50                                       Example 10 58       58        58     43                                       Example 11 57       57        57     42                                       Example 13 59       59        59     42                                       Example 14 62       62        62     46                                       Example 15 60       60        60     48                                       Example 12 61       61        60     44                                       Example 8  58       58        58     41                                       Example 9  57       57        57     40                                       Example 11 59       59        57     38                                       Ex. 8:Ex. 1 (7:3)                                                                        59       59        59     54                                       Ex. 15:Ex. 1 (8:2)                                                                       58       58        57     52                                       Ex. 15:Ex. 1 (8:2)                                                                       61       61        61     52                                       Ex. 15:Ex. 1 (7:3)                                                                       62       62        62     51                                       ______________________________________                                    

As will be seen from the results set forth in Table 3, it was found thatthe derivatives of naphthalocyanine used in the present invention couldretain the initial CN ratios after the repeated reproduction of 10⁶times at 1.4 mW, although the CN ratios were gradually lowered when anextremely intensive reproducing beam of 1.6 mW was used.

COMPARATIVE EXAMPLE 4

The durability to reproducing laser beams of the optical recordingmedium prepared by Comparative Example 2 was appraised similarly toExample 17. The result revealed that the CN ratio began to lower afterthe repeated reproduction of 10⁴ times when a reproducing laser beam of1.0 mW was used and tracking cound not be traced after the repeatedreproduction of 10⁵ times.

We claim:
 1. A derivative of naphthalocyanine containing aperfluoroalkyl group and represented by the following formula (I) of;##STR15## wherein n₁, n₂, n₃ and n₄ each stand for an integer of from 0to 2, and n₁ +n₂ +n₃ +n₄ ≠0; and n₅ stands for an integer of from 1 to10.
 2. A derivative of naphthalocyanine containing a perfluoroalkylgroup and represented by the following formula (II) of; ##STR16##wherein M stands for (R)₃ SiO--Si--OSi(R)₃ or [F(CF₂)_(n).sbsb.5 --(R)₂SiO--Si--OSi(R)₃ where R is an alkyl group having 1 to 10 carbon atoms;n₁, n₂, n₃ and n₄ each stand for an integer of from 0 to 2 and n₅ standsfor an integer of from 1 to 10, n₁ +n₂ +n₃ +n₄ ≠0 when M is (R)₃SiO--Si--OSi(R)₃.